This invention relates to treatment of composite polyamide reverse osmosis membranes. More specifically, treatment of polyamide membranes to enhance rejection of certain acids and organic materials in a reverse osmosis process is contemplated.
Removal of materials dissolved or dispersed in a solution by separation of these materials from the dispersing medium or solvent utilizing reverse osmosis membranes is well known. The membranes used for reverse osmosis are selectively permeable to certain components of the mixture to be separated. Generally, water is the component to which such membranes are especially permeable. An aqueous feed solution is conveniently brought in contact with one surface of the reverse osmosis membrane under pressure so as to effect selective permeation of water through the membrane. This process is most generally used for desalination of water-containing salts. However, reverse osmosis has also been used to separate organic compounds and other materials from aqueous feed solutions.
The performance of reverse osmosis membranes has a critical effect on the efficiency and efficacy of reverse osmosis processes. Advantageously, the reverse osmosis membrane should be relatively impermeable to materials which are to be separated from the water and highly permeable to water. It has been found that membranes having a porous support which provides physical strength but imparts little or no rejection, combined with a thin dsscriminating layer adherent to the support, are particularly useful. Such membranes are commonly referred to as thin film composite membranes.
Polyamide membranes have been widely employed in reverse osmosis processes. U.S. Pat. No. 4,277,344 describes a variety of membranes having a polyamide discriminating layer on a porous support. These membranes are preferably prepared by interfacial polymerization of a difunctional aromatic amine such as meta-phenylene diamine and a trifunctional aromatic acyl halide, such as trimesoyl chloride, optionally containing difunctional acyl halide. A 1,3,5-cyclohexane tricarbonyl chloride can also be employed as the acyl halide reactant. Such membranes are further illustrated in U.S. Pat. Nos. 4,520,044 and 4,606,943. European Patent Application Publication No. 211,633 also describes composite polyamide membranes.
The treatment of membranes to enhance performance is described in the prior art in a number of patents. U.S. Pat. No. 3,551,331 describes a process for modifying the permeability of a substantially linear aliphatic polyamide membrane. In this process, the polyamide membrane is treated with a protonic acid, lyotropic salt or a Lewis acid.
U.S. Pat. No. 3,877,978 describes use of copolymers of vinyl acetate with various ethylenically unsaturated carboxylic acids to enhance the rejection of certain semi-permeable membranes.
U.S. Pat. No. 3,886,066 discloses the use of hydrolyzable tannins to reduce the salt passage through semi-permeable membranes.
U.S. Pat. No. 3,951,815 describes a composite semi-permeable membrane formed of an ultrathin film of polyethylenimine on a support, where said film has been crosslinked with difunctional or trifunctional acylhalides, chloroformates, isocyanates and sulfonyl chlorides.
U.S. Pat. No. 4,214,020 describes a process for coating exteriors of hollow fiber membranes to enhance their membrane characteristics.
U.S. Pat. No. 4,634,531 describes the use of sequential treatment with a water-soluble amine and a water-soluble aldehyde to improve selective permeation.
U.S. Pat. No. 4,704,324 teaches preparation of membranes by reaction of a nucleophilic first compound with a second compound bearing reactive onium groups.
U.S. Pat. No. 4,812,238 describes the treatment of composite polyamide membranes with nitrous acid or a diazonium compound. The nitrous acid is disclosed to react with pendant amine groups.
U.S. Pat. No. 4,828,700 discloses that reverse osmosis membranes can be treated with polymers bearing carboxylic acid groups and optionally pendant hydroxyl or amide moieties to enhance salt rejection.
U.S. Pat. No. 3,904,519 describes treatment of linear aromatic polyamides with certain crosslinking reagents to improve flux or flux stability of the resulting membranes. Crosslinking reagents employed include aldehydes, polyamines, polycarboxylic acids, polyisocyanates, oxidizing agents, peroxides and other compounds.
Existing commercial composite polyamide membranes display a good combination of high water flux, good salt rejection and acceptable chemical stability. Membranes which are more tolerant of acidic or basic conditions and which demonstrate a higher rejection for organic materials while maintaining high water flux are still sought.